JPH03220261A - Modifier and polyester composition - Google Patents

Abstract

PURPOSE:To prepare a modifier capable of improving the melt flow properties and appearance of a polyester resin molding when compounded into the resin by combining two compds. each represented by a specific formula in a specified ratio. CONSTITUTION:95-99.99wt.% compd. of formula I and 0.01-5wt.% compd. of formula II are combined to give a modifier for a polyester resin. In the formulas, R is a residue of an arom. alcohol or phenol; A is 1-4C alkylene; m is 10-50; and Me is methyl. The addition of the modifier to a polyester resin gives a polyester compsn. which has improved melt flow properties, gives a molded article with a good appearance, and hence can be widely used for molding various molded articles, containers, etc., in applications esp. for electrical parts, building parts, automotive parts as well as for fiber, film, and sheet.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to modifiers and polyester compositions.

[Prior Art] Conventionally, polyester resin compositions comprising polyethylene terephthalate, glass fiber, sodium salt of ethylene/methacrylic acid copolymer, and polyethylene glycol dimethyl ether are known. (For example, Japanese Patent Application Laid-Open No. 59-24747.) [Problems to be Solved by the Invention] However, the above-mentioned polyester resin composition did not satisfy all of the fluidity during melting and the appearance during molding. .

[Means for Solving the Problems] The present inventors have conducted intensive studies on a modifier that improves fluidity during melting and provides a composition with a good appearance during molding, and a polyester resin composition using the modifier. As a result, we have arrived at the present invention.

That is, the present invention is based on the weight of the modifier.
9.99% by weight of the compound represented by the general formula (1) and R-○-Fang AO-+-rMe (1) 0.01 to 5% by weight of the compound R represented by the general formula (2)
-0-fA A polyester resin modifier consisting of OhH (2) (wherein R is an aromatic alcohol or phenol residue, A is a carbon number of 1
~4 alkylene group, m is an integer N Me of 10 to 50
is a methyl group): and 60 to 9 based on the weight of the composition.
9.8% polyester resin and 0. 2-40%
A polyester resin composition comprising the modifier according to claim 1.

In general formulas (1) and (2), the aromatic alcohols constituting the aromatic alcohol residue of R include benzyl alcohol, phenylethyl alcohol, hydrocinnamyl alcohol, methylbenzyl carbinol,
Ethyl phenyl carbinol, phenyl ethylene glycol, etc., and hydrogen in their nucleus or alkyl group is a halogen element (CI).

Br, etc.).

Phenols include phenol, (substituted) alkylphenols (cresol, ethylphenol, propylphenol, butylphenol).

octylphenol, nonylphenol, dinonylphenol, cumylphenol, etc.), styrenation (1-2
Examples include phenol (0 mole), styrenated (1 to 20 mole) cumylphenol, naphthol, etc., and those in which the hydrogen of their nucleus or alkyl group is substituted with a halogen element (CI, Br, etc.).

Preferred aromatic alcohols and phenols are benzyl alcohol and phenol.

Naphthol, a styrenated (1-3 mole) phenol.

Examples of the alkylene group having 1 to 4 carbon atoms in A include methylene, ethylene, propylene, and butylene groups. Preferred are ethylene and propylene groups.

A forms an AO (oxyalkylene group) together with an oxygen atom, and the m AOs may be the same or different, and the bond format may be random or block. m is usually lO~5
01 Preferably an integer from 15 to 35.

Examples of compositions of modifiers having general formulas (1) and (2) are listed below. Based on the weight of the modifier, 99.8% by weight terminal methyl etherification of 25 mole adduct of benzyl alcohol ethylene oxide and 0.2% by weight of 25 mole adduct of benzyl alcohol ethylene oxide; benzyl alcohol ethylene oxide, propylene oxide random 99.7 weight 1t% terminal methyl etherified adduct (ethylene oxide 15 moles, propylene oxide 10 moles) and benzyl alcohol ethylene oxide, propylene oxide random adduct (ethylene oxide 15 moles, propylene oxide 10 moles) 0.3 weight %: Phenol ethylene oxide 3
0 mole adduct terminal methyl etherified product 99.9% by weight
and 30 mole adduct of phenol ethylene oxide 0
．． 1% by weight; 99.7% by weight of terminal methyl etherified product of 20 mole naphthol ethylene oxide adduct and 0.0% by weight of naphthol ethylene oxide adduct. 3% by weight;
Styrenated (2 mol) phenol ethylene oxide 2
99.8% by weight of terminal methyl etherified product of 2 molar adduct
and 0.22 mole adduct of styrenated (2 mole) phenol ethylene oxide. 2% by weight; styrenated (3 mol) phenol propylene oxide 5 mol, ethylene oxide 15 mol block adduct terminal methyl etherified product 99.7% by weight and styrenated (3 mol) phenol propylene oxide 5 mol, ethylene oxide 15 mol Block adduct 0. 3% by weight etc.

The modifier of the present invention is obtained by adding alkylene oxide to aromatic alcohols and phenols, and converting the terminals into methyl ether.

In the modifier of the present invention, the compound of general formula (1) is 9
If 5% by weight is ungrooved, the fluidity and appearance during molding of the polyester resin composition will be poor, and the physical properties (flexural strength, tensile strength) of the molded product will also be reduced. The compound of general formula (1) is 9
It is difficult to industrially produce a content exceeding 9.99% by weight.

The modifier of the present invention may contain other modifiers as necessary in addition to the compounds of general formulas (1) and (2).

Other modifiers include inorganic solid substances such as talc, metal salts of inorganic and organic acids, metal glycolates, and the like. In this case, the amount of other modifiers is usually 10 weight or less, based on the total weight of the modifier of the present invention and other modifiers.

In the present invention, the polyester resin has at least 5
It is obtained by directly esterifying a dicarboxylic acid component in which 0 mol% is terephthalic acid and a diol component in which at least 50 mol% is ethylene glycol, or by polycondensation after transesterification.

As a dicarboxylic acid component other than terephthalic acid, carbon number 6
~14 Te, aromatic dicarboxylic acid other than phthalic acid (e.g. phthalic acid, isophthalic acid, 2゜6-naphthalene dicarboxylic acid, 4.4-diphenyldicarboxylic acid, diphenylethane-4,4-dicarboxylic acid, etc.), carbon Number 4~
8 aliphatic dicarboxylic acids (for example, adipic acid, sebacic acid, etc.) or alicyclic dicarboxylic acids having 8 to 12 carbon atoms (for example, cyclohexanedicarboxylic acid, etc.).

Other diol components other than ethylene glycol include other aliphatic diols having 3 to 10 carbon atoms (e.g. propane-1,
3-diol, butane-1,4-diol, pentane-
1,5-diol, hexane-1,6-diol, etc.)
, other alicyclic diols having 6 to 15 carbon atoms (e.g. cyclohexane-1°4-dimetatool, etc.), 6 to 1 carbon atoms
2, aromatic diols (eg, bisphenol A, etc.) or polyhydric phenols (eg, hydroquinone, etc.).

Furthermore, an oxycarboxylic acid (for example, ε-oxycaproic acid, hydroxybenzoic acid, etc.) or the like may be copolymerized in an amount of 10 mol % or less of the total of the dicarboxylic acid component and the diol component. Of course, the polyester resin may also be branched with trihydric or tetrahydric alcohols (e.g. trimethylolpropane, pentaerythritol, etc.) or tribasic or tetrabasic acids (e.g. trimesic acid, trimellitic acid, etc.). From an industrial viewpoint, polyester resins are preferably polyethylene terephthalate resins, polypropylene terephthalate resins, and polybutylene terephthalate resins. Its shape may be fibrous or pellet-like.

If necessary, a reinforcing filler can be added to the composition of the present invention to further improve its physical properties. Suitable reinforcing fillers include glass fibers, mineral fibers, talc, mica, kaolin, and the like.

Further, a flame retardant can be added to the composition of the present invention to impart flame retardancy, if necessary. Suitable flame retardants include halogenated diphenyl ether compounds, halogenated polycarbonate compounds, halogenated polyphenylene oxide compounds, halogenated bisphenol-type resins, S-triazine-containing compounds, halogenated polystyrene compounds, Examples include red phosphorus flame retardants, and if necessary, flame retardant aids such as antimony trioxide and zinc oxalate may be added to these to develop a synergistic effect.

Furthermore, other additives such as thermal antioxidants, light stabilizers, pigments, dyes, nucleating agents, plasticizers, lubricants, etc. may be added to the extent that the physical properties are not impaired.

The amount of reinforcing filler added is usually O to 70%, and the amount of flame retardant added is usually O to the weight of the polyester resin composition.
-20%, and the amount of flame retardant aid added is usually 0-15%.

The method for producing the composition of the present invention is not particularly limited, but preferably includes a pellet-shaped polyester resin and a modifier, optionally a reinforcing filler, a flame retardant, a flame retardant aid,
It can be easily formed by a conventional method such as pre-kneading and other additives and extrusion molding or injection molding. For example, an extruder: Brabender kneader Banbury mixer or other various mixers can be used for kneading, and the kneading temperature ranges from above the melting point of commonly used polyester resins to below 300°C, preferably from 260°C to 28°C.
It is 0°C.

Alternatively, the composition of the invention can be obtained by adding the modifier of the invention during polyester polymerization.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

Parts in the examples are parts by weight.

Example 1 108 parts of benzyl alcohol in a 2L autoclave and a caustic force of U0. After adding 2 parts of ethylene oxide and purging with nitrogen, 1100 parts of ethylene oxide was successively introduced at a temperature of 140° C. over 6 hours with stirring. After the reaction was completed, 120 parts of caustic soda was added, and after purging with nitrogen, 110 parts of methyl chloride was successively introduced at a temperature of 100° C. over 5 hours with stirring, and the mixture was aged at that temperature for 5 hours. Next, excess alkali, salt, water, etc. were removed by a conventional method to obtain 1200 parts of Modifier No. 1 of the present invention. Based on the 0OH value, the composition of Modifier No. 1 was Modifier No.

Terminal methyl etherified product of 25 mole adduct of benzyl alcohol ethylene oxide based on the weight of
Weight%, benzyl alcohol ethylene oxide 2.5
The molar adduct was 0.02% by weight.

Example 2 108 parts of benzyl alcohol and 0.2 parts of caustic potassium were placed in a 2L autoclave, the atmosphere was replaced with nitrogen, and a mixture of 660 parts of ethylene oxide and 5,800 parts of propylene oxide was stirred at a temperature of 1.

The introduction was carried out sequentially over a period of 8 hours at 30°C. After the reaction was completed, 120 parts of caustic soda was added, and after purging with nitrogen, 110 parts of methyl chloride was successively introduced at a temperature of 100° C. over 5 hours with stirring, and the mixture was aged at that temperature for 5 hours. Next, remove excess alkali, salt, water, etc. using the usual method,
The composition of Modifier No. 2 is Modifier No. 2 based on the 0 OH value obtained from 1300 parts of Modifier No. 12 of the present invention.

Benzyl alcohol ethylene oxide, propylene oxide random adduct (15 moles of ethylene oxide, 10 moles of propylene oxide) based on the weight of 2
The terminal methyl etherified product was 99% by weight, 7% by weight, and the random adduct of benzyl alcohol ethylene oxide and propylene oxide (ethylene oxide 15 mol, propylene oxide 10 mol) was 0.03% by weight.

Example 3 94 parts of phenol and 03 parts of caustic potassium in a 2L autoclave
．． After adding 2 parts and replacing with nitrogen, ethylene oxide 13
20 parts were successively introduced over 6 hours at a temperature of 180° C. with stirring. After the reaction was completed, 120 parts of caustic soda was added, and after purging with nitrogen, 110 parts of methyl chloride was successively introduced at a temperature of 100° C. over 5 hours with stirring. It was aged for 5 hours at that temperature. Next, excess alkali, salt, moisture, etc. are removed by a normal method, and the modifier No. of the present invention is obtained.
, the composition of 3 is the modifier No. from the 0OH value obtained from 1350 parts of 3.

Phenol ethylene oxide based on the weight of 30
99.9% by weight of terminal methyl etherified product of molar adduct;
Phenol ethylene oxide 25 mole adduct 0.01
% by weight.

Example 4 44 parts of β-naphtholt and 0.0 parts of caustic potassium were placed in a 2L autoclave. After adding 2 parts of ethylene oxide and purging with nitrogen, 880 parts of ethylene oxide was successively introduced at a temperature of 160° C. over 6 hours while stirring. After the reaction is completed, caustic soda 1
．． After adding 20 parts and replacing with nitrogen, methyl chloride 11
0 part was gradually introduced into the solution four times at a temperature of 100° C. for 5 hours while stirring and stirring. It was aged for 5 hours at that temperature. Next, remove excess alkali, salt, water, etc. using the usual method,
To and oo parts of modifier No. 4 of the present invention were obtained.

Based on the OH value, the composition of modifier N004 is modifier No.

Based on the weight of 4, the terminal methyl etherified product of 20 moles of β-naphthol ethylene oxide adduct was 99.7% by weight, and the 20 mole adduct of β-naphthol ethylene oxide was 0.03% by weight.

Example 5 104 parts of phenol and 3 parts of aluminum chloride (catalyst) were placed in a 1L Kolben, and the atmosphere was replaced with nitrogen.) 251 parts of styrene monomer was added dropwise over 4 hours at a temperature of 100°C while stirring, and the mixture was heated at that temperature for 1 hour. Aged. Remove the catalyst etc. by the usual method, and styrenated (2 mol) phenol 31
Got 22 copies.

322 parts of styrenated (2 mol) phenol and 0.2 part of caustic potassium were placed in a 2L autoclave, and the atmosphere was purged with nitrogen, followed by successive introduction of ethylene oxide 9EL 8 parts at a temperature of 160°C over 6 hours with stirring.

I entered. After the reaction was completed, 1201 parts of caustic soda was added, and after purging with nitrogen, 110 parts of methyl chloride was successively introduced at a temperature of 100° C. over 5 hours with stirring. It was aged for 5 hours at that temperature. Next, excess alkali IJ Th salt, moisture, etc. were removed by a conventional method, and 1250 parts of Modifier No. 5 of the present invention was obtained. From the 0OH value, Modifier No. 95 was obtained.
The composition is Modifier No.

99.8% by weight of the terminal methyl etherified adduct of 22 moles of styrenated (2 moles) phenol ethylene oxide and 0.02% by weight of the 22 moles adduct of styrenated (2 moles) phenol ethylene oxide. Ta.

Example 6 104g of phenol in 1L Kolben! After adding 4 parts of aluminum i-chloride (catalyst, medium) and purging with nitrogen, 376 parts of styrene monomer was added dropwise over 4 hours at 100° C. with stirring, and the mixture was aged at that temperature for 1 hour. Remove the catalyst etc. by the usual method, and remove the styrenated (3 mol) ferroene, nor 4.
3EllJl.

Styrenated, (3 mol) pheno, in a 2L autoclave.
After adding 36 parts of 4F and 2 parts of IJO and replacing the mixture with nitrogen, 290 parts of propylene oxide was successively introduced at a temperature of 110 DEG C. over 8 hours with stirring. Furthermore, 660 parts of ethylene oxide was successively introduced at a temperature of 130° C. over 6 hours while stirring. After the reaction was completed, 120 parts of caustic soda was added, the atmosphere was replaced with nitrogen, and 110 parts of methyl chloride was heated at 100°C with stirring for 5 minutes.
It was introduced gradually over time. It was aged for 5 hours at that temperature.

Next, excess alkali, salt, moisture, etc. were removed by a conventional method to obtain 1350 parts of Modifier No. E3 of the present invention. Based on the 0 oH value, the composition of Modifier No. 8 was Modifier No.

Based on the weight of 6, styrenated (3 mol) phenol, 5 mol of propylene oxide, 15 mol of ethylene oxide, terminal methyl etherified product of rubroc adduct 9.9.
, 7% by weight, styrenated (3 moles) phenol, 5 moles of propylene oxide, 15 moles of ethylene oxide, 0.03 moles of pro-tox adduct. It was 1% by weight.

Examples 7 to 12 100 parts of polyethylene terephthalate resin, 50 parts of glass fiber, and 3 parts of modifiers No., L to 6 of the present invention were pre-kneaded, extruded and kneaded, and then injection molded at a mold temperature of 90°C. A polyester composition of the present invention was obtained. Table 1 shows the test results for kneading torque, appearance of molded products, bending strength, and tensile strength.

Comparative Example 1.2 As a comparative example, molding was performed under the same conditions as Examples 7 to 12 in the case of not using a modifier (Comparative Example 1) and the case of using polyethylene glycol dimethyl ether as a modifier (Comparative Example 2). The results for the polyester compositions tested are also shown in Table 1.

Comparative Examples 3 to 8 As comparative examples, the following compositions (No, 1' to No,
Table 2 shows the results for polyester compositions that were molded under the same conditions as Examples 7 to 12 using 8').

No. 1': A modifier consisting of 85% by weight of a terminal methyl etherified product of a 25 mol adduct of benzyl alcohol ethylene oxide and 15% by weight of a 25 mol adduct of benzyl alcohol ethylene oxide.

No. 2': 80% by weight of terminal methyl etherified product of benzyl alcohol ethylene oxide, propylene oxide random adduct (ethylene oxide 15 mol, propylene oxide 10 mol) and benzyl alcohol ethylene oxide, propylene oxide random adduct (ethylene oxide 15 mol) Modifier consisting of 20% by weight (mol, 10 moles of propylene oxide).

No. 3': A modifier consisting of 90% by weight of a terminal methyl etherified product of a 30 mole adduct of phenol ethylene oxide and 10% by weight of a 25 mole adduct of phenol ethylene oxide.

No. 4': A modifier consisting of 82% by weight of a terminal methyl etherified product of a 20 mol adduct of β-naphthol ethylene oxide and 18% by weight of a 20 mol adduct of β-naphthol ethylene oxide.

No, 5': Styrenated (2 mol) phenol ethylene oxide 2
2 mol adduct/terminal methyl etherified product 88% by weight and styrenated (2 mol) phenol ethylene oxide 2
Modifier consisting of 12% by weight of 2 molar adduct.

No. 8': Styrenated (3 mol) phenol propylene oxide 5 mol, ethylene oxide 15 mol block adduct terminal methyl etherified product 83% by weight and styrenated (3 mol) phenol propylene oxide 5 mol, ethylene oxide 15 mol block Modifier consisting of 17% by weight of adduct.

Table 1 Table 2 The polyester resin compositions can be widely used for molding various molded parts, pipes, containers, etc., and are especially suitable for electrical parts, building material parts, automobile parts, etc., and can be used for fibers, films, sheets, etc. It can also be used for

[Effects of the Invention] The polyester resin composition of the present invention solves the problem of poor fluidity during molding that conventional compositions have.
The fluidity at the time of melting and the appearance at the time of molding are all satisfactory, and the molded product has excellent ease of molding and surface appearance of the molded product. Furthermore, there is no deterioration in the mechanical properties of the molded product.

Claims (1)

[Claims] 1. 95 to 99.99% by weight based on the weight of the modifier
The compound represented by the general formula (1) and R-O■AO■
_mMe(1) 0.01 to 5% by weight of the compound R represented by the general formula (2)
-O■AO_mH(2) (wherein, R is a residue of aromatic alcohol or phenol, A is an alkylene group having 1 to 4 carbon atoms, and m is 10 to 5
An integer of 0, Me is a methyl group) A modifier for polyester resin. 2. A polyester resin composition comprising 60 to 99.8% of the polyester resin and 0.2 to 40% of the modifier according to claim 1, based on the weight of the composition.